U.S. patent application number 16/100586 was filed with the patent office on 2018-12-06 for solid electrolyte containing oxynitride, and secondary battery including the solid electrolyte.
The applicant listed for this patent is Panasonic Intellectual Property Management Co., Ltd.. Invention is credited to Yu NISHITANI, Satoshi SHIBATA, Takuji TSUJITA.
Application Number | 20180351208 16/100586 |
Document ID | / |
Family ID | 57460407 |
Filed Date | 2018-12-06 |
United States Patent
Application |
20180351208 |
Kind Code |
A1 |
SHIBATA; Satoshi ; et
al. |
December 6, 2018 |
SOLID ELECTROLYTE CONTAINING OXYNITRIDE, AND SECONDARY BATTERY
INCLUDING THE SOLID ELECTROLYTE
Abstract
A solid electrolyte includes an oxynitride that contains an
alkaline-earth metal, phosphorus, oxygen, and nitrogen. A P2p
spectrum obtained by an X-ray photoelectron spectroscopy
measurement of the oxynitride contains a peak component originating
from a P--N bond.
Inventors: |
SHIBATA; Satoshi; (Osaka,
JP) ; NISHITANI; Yu; (Osaka, JP) ; TSUJITA;
Takuji; (Osaka, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Panasonic Intellectual Property Management Co., Ltd. |
Osaka |
|
JP |
|
|
Family ID: |
57460407 |
Appl. No.: |
16/100586 |
Filed: |
August 10, 2018 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
15371063 |
Dec 6, 2016 |
10074872 |
|
|
16100586 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C23C 16/45555 20130101;
C23C 16/308 20130101; H01M 10/0562 20130101; H01M 10/054 20130101;
C23C 16/45531 20130101; Y02E 60/10 20130101; H01M 2300/0071
20130101; C23C 16/45561 20130101 |
International
Class: |
H01M 10/0562 20060101
H01M010/0562; C23C 16/455 20060101 C23C016/455; H01M 10/054
20060101 H01M010/054 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 4, 2016 |
JP |
2016-132614 |
Aug 19, 2016 |
JP |
2016-161513 |
Claims
1. A solid electrolyte including an oxynitride that contains
magnesium, phosphorus, oxygen, and nitrogen, wherein a molar ratio
of the magnesium to the phosphorus is higher than a molar ratio of
the nitrogen to the phosphorus, and a P2p spectrum obtained by an
X-ray photoelectron spectroscopy measurement of the oxynitride
contains a peak component originating from a P--N bond.
2. The solid electrolyte according to claim 1, wherein the
oxynitride has magnesium ion conductivity.
3. The solid electrolyte according to claim 1, wherein the
oxynitride is magnesium phosphorus oxynitride.
4. The solid electrolyte according to claim 1, further including
MgO.
5. The solid electrolyte according to claim 1, wherein a molar
ratio of the oxygen to the phosphorus is higher than the molar
ratio of the magnesium to the phosphorus.
6. The solid electrolyte according to claim 1, wherein the molar
ratio of the nitrogen to the phosphorus is equal to or more than
0.2 and less than 1.
7. The solid electrolyte according to claim 1, wherein the molar
ratio of the magnesium to the phosphorus is equal to or more than
1.5.
8. The solid electrolyte according to claim 1, wherein the molar
ratio of the magnesium to the phosphorus is equal to or more than
1.11 and equal to or less than 1.97.
9. The solid electrolyte according to claim 1, wherein an O1s
spectrum obtained by the X-ray photoelectron spectroscopy
measurement of the oxynitride contains a first peak component
originating from a P--O bond and a second peak component
originating from an Mg--O bond, and
10. The solid electrolyte according to claim 1, wherein an N s
spectrum obtained by the X-ray photoelectron spectroscopy
measurement of the oxynitride contains a first peak component
originating from triply coordinated nitrogen and a second peak
component originating from doubly coordinated nitrogen, and an
intensity of the second peak component is higher than or equal to
an intensity of the first peak component.
11. The solid electrolyte according to claim 1, wherein, in the P2p
spectrum, an intensity of the peak component originating from the
P--N bond is 0.1% or more of an intensity of a peak component
originating from a P--O bond.
12. A secondary battery comprising: a positive electrode; a
negative electrode; and the solid electrolyte according to claim
1.
13. The secondary battery according to claim 12, wherein the solid
electrolyte presents as a film disposed between the positive
electrode and the negative electrode.
14. The secondary battery according to claim 11, wherein the
positive electrode has an irregular surface, and the film is in
direct contact with the irregular surface while following a shape
of the irregular surface.
15. The secondary battery according to claim 11, wherein the
negative electrode has an irregular surface, and the film is in
direct contact with the irregular surface while following a shape
of the irregular surface.
16. The secondary battery according to claim 12, wherein the
positive electrode contains active material particles, and the
solid electrolyte presents as coating films covering the respective
active material particles.
17. The secondary battery according to claim 12, wherein the
negative electrode contains active material particles, and the
solid electrolyte presents as coating films covering the respective
active material particles.
18. The secondary battery according to claim 12, further
comprising: a liquid electrolyte containing magnesium salt.
19. A device comprising: a first electrode; a second electrode; and
the solid electrolyte according to claim 1, that extends from the
first electrode to the second electrode, wherein the solid
electrolyte includes a first region close to the first electrode, a
second region at a center between the first electrode and the
second electrode, and a third region close to the second electrode,
and the molar ratio of the magnesium to the phosphorus in the first
region is higher than those in the second region and in the third
region.
Description
RELATED APPLICATIONS
[0001] This application is a Continuation of application Ser. No.
15/371,063, filed Dec. 6, 2016, which claims the benefit of
priority to Japanese Application No. 2016-132614, filed Jul. 4,
2016 and Japanese Application No. 2016-161513, filed Aug. 19, 2016,
the disclosures of which are incorporated in their entirety by
reference herein.
BACKGROUND
1. Technical Field
[0002] The present disclosure relates to a solid electrolyte
containing an oxynitride and a secondary battery including the
solid electrolyte.
2. Description of the Related Art
[0003] In recent years, secondary batteries using polyvalent ions
as mobile ions have been investigated.
SUMMARY
[0004] One non-limiting and exemplary embodiment provides a novel
solid electrolyte containing alkaline-earth metal.
[0005] In one general aspect, the techniques disclosed here feature
a solid electrolyte including an oxynitride that contains an
alkaline-earth metal, phosphorus, oxygen, and nitrogen. A P2p
spectrum obtained by an X-ray photoelectron spectroscopy
measurement of the oxynitride contains a peak component originating
from a P--N bond.
[0006] It should be noted that comprehensive or specific
embodiments may be implemented as a second battery, or method.
[0007] Additional benefits and advantages of the disclosed
embodiments will become apparent from the specification and
drawings. The benefits and/or advantages may be individually
obtained by the various embodiments and features of the
specification and drawings, which need not all be provided in order
to obtain one or more of such benefits and/or advantages.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a diagram of an example of the configuration of a
reaction apparatus for producing solid electrolyte according to an
embodiment;
[0009] FIG. 2A is a flowchart showing an example of a method for
producing a solid electrolyte according to an embodiment;
[0010] FIG. 2B is a flowchart showing an example of a method for
producing a solid electrolyte according to an embodiment;
[0011] FIG. 2C is a flowchart showing an example of a method for
producing a solid electrolyte according to an embodiment;
[0012] FIG. 3 is a graph showing P2p spectra obtained by measuring
a solid electrolyte in Example 1, a solid electrolyte in Example 2,
and magnesium phosphate (Mg.sub.3(PO.sub.4).sub.2) by XPS;
[0013] FIG. 4A is a graph showing O1s spectra obtained by measuring
the solid electrolytes in Examples 1 and 2 by XPS;
[0014] FIG. 4B is a graph showing O1s spectra obtained by measuring
a solid electrolyte in Example 3, a solid electrolyte in Example 4,
and a solid electrolyte according to a reference example by
XPS;
[0015] FIG. 5 is a graph showing N1s spectra obtained by measuring
the solid electrolytes in Examples 1 and 2 by XPS;
[0016] FIG. 6 is a graph showing the temperature dependence of the
ionic conductivity of the solid electrolytes in Examples 1 and
2;
[0017] FIG. 7A is an illustration showing a transmission electron
microscope (TEM) image of a sample including an MgPON film in
Example 1;
[0018] FIG. 7B is an enlarged view of a portion surrounded by a
dotted line in FIG. 7A; and
[0019] FIG. 8 is an illustration showing an enlarged view of a
portion surrounded by a dotted line in FIG. 7B;
[0020] FIG. 9 is a cross-sectional diagram showing an exemplary
structure of a secondary battery.
DETAILED DESCRIPTION
Underlying Knowledge Forming Basis of the Present Disclosure
[0021] Knowledge obtained by the inventors will be described
below.
[0022] Solid electrolytes have higher ionic resistance as compared
to typical electrolyte solutions. The resistance between a positive
electrode active material and a solid electrolyte and the
resistance of the interface between the solid electrolyte and a
negative electrode active material are also high. Therefore, as the
thickness of a solid electrolyte layer is larger, the internal
resistance of a battery is higher and the voltage drop is larger;
hence, it is difficult to obtain good charge/discharge
characteristics at a large current. As a result, for example, a
problem that the charge time is long is caused.
[0023] Therefore, a solid electrolyte practically used in, for
example, lithium ion secondary batteries is limited. A solid
electrolyte containing a divalent or higher valent metal is not in
practical use.
[0024] An embodiment of the present disclosure can provide a solid
electrolyte containing an oxynitride containing a divalent metal
element.
[0025] An oxynitride according to an aspect of the present
disclosure can be applied to, for example, a solid electrolyte
layer of an all-solid-state battery. For example, when the ionic
conductivities of solid electrolytes are equal, the amount of
charge that moves when a divalent metal ion moves is twice the
amount of charge that moves when a monovalent metal ion moves. That
is, a secondary battery containing a solid electrolyte containing
divalent metal ions as mobile ions can be increased in theoretical
capacity as compared to a secondary battery containing a solid
electrolyte containing monovalent metal ions as mobile ions.
EMBODIMENTS
[0026] Solid electrolytes according to various embodiments, methods
for producing the solid electrolytes, and secondary batteries
containing the solid electrolytes are exemplified below. As shown
in the present disclosure, materials, compositions, thicknesses,
shapes, characteristics, steps of each production method, and the
order of the steps are for exemplification only. A plurality of
steps of a production method may be performed concurrently or in
different periods.
[0027] An oxynitride film and a method for producing the same are
mainly described below. Incidentally, the oxynitride film is an
example of a "solid electrolyte containing an oxynitride". A solid
electrolyte according to the present disclosure is not limited to
any film. In the present disclosure, magnesium phosphorus
oxynitride is referred to as "MgPON" in some cases for convenience
of description and is not limited to a specific composition
ratio.
1. PRODUCTION APPARATUS
[0028] FIG. 1 shows an example of the configuration of a production
apparatus 1 for forming an oxynitride film according to an
embodiment by an atomic layer deposition (ALD) process. The
production apparatus 1 includes a reactor 2, a controller 15, a
first precursor supply section 3, a second precursor supply section
4, an oxygen supply section 12, a nitrogen supply section 13, and a
purge gas supply section 14.
[0029] The reactor 2 is, for example, a process chamber.
[0030] The first precursor supply section 3 supplies a first
precursor into the reactor 2. The first precursor contains network
formers. The first precursor supply section 3 is, for example, a
bottle for holding the first precursor. In the present disclosure,
the term "precursor" means source material for ALD process.
[0031] The second precursor supply section 4 supplies a second
precursor into the reactor 2. The second precursor contains
alkaline-earth metal. The second precursor supply section 4 is, for
example, a bottle for holding the second precursor.
[0032] The production apparatus 1 further includes a first pipe P1
extending from the first precursor supply section 3 to the reactor
2 and a second pipe P2 extending from the second precursor supply
section 4 to the reactor 2.
[0033] The oxygen supply section 12 supplies an oxygen gas and/or
an ozone gas into the reactor 2. The nitrogen supply section 13
supplies a nitrogen gas and/or an ammonia gas into the reactor 2.
The purge gas supply section 14 supplies a purge gas into the
reactor 2 to purge gases remaining in the reactor 2.
[0034] The production apparatus 1 further includes auxiliary gas
supply sections 7 to 10, mass flow controllers 5a to 5e, valves V1
to V7, manual valves MV1 to MV3, ant a needle valve NV as shown in
FIG. 1.
[0035] The controller 15 controls, for example, the valves V1 to V7
and the mass flow controllers 5a to 5e. The controller 15 includes,
for example, a memory and a processor. The controller 15 further
includes, for example, a semiconductor device, a semiconductor
integrated circuit (IC), and a large scale integration (LSI) or an
electronic circuit which is a combination of the semiconductor
device, the IC, and the LSI. The LSI or the IC may be integrated in
a single chip or may be composed of a plurality of chips. For
example, each functional block may be integrated in a single chip.
The LSI and the IC may be called, for example, a system LSI, a very
large scale integration (VLSI), or an ultra-large scale integration
(UVLSI) depending on the degree of integration.
[0036] A commercially available product may be applied to the
production apparatus 1 depending on the type of a target oxynitride
film. Commercially available production apparatuses include, for
example, those, such as Savannah Systems, Fuji Systems, and Phoenix
Systems, available from Ultratech/Cambridge NanoTech; those, such
as ALD-series, available from Showa Shinku Co., Ltd.; those, such
as TFS 200, TFS 500, TFS 120P 400A, and P800, available from Beneq;
those, such as OpAL and FlexAL, available from Oxford Instruments;
those, such as InPassion ALD 4, InPassion ALD 6, and InPassion ALD
8, available from SoLay Tec; those, such as AT-400 ALD System,
available from ANRIC TECHNOLOGIES; and those, such as LabNano and
LabNano-PE, available from Ensure NanoTech. In the case where the
commercially available product is applied to the production
apparatus 1, for example, a program for executing various flows
below is stored in the memory in the controller 15 and is executed
by the processor in the controller 15, whereby the production
apparatus 1 can be operated in this embodiment.
2. PRODUCTION METHOD
[0037] A method for producing the oxynitride film using the
production apparatus 1 will be described below as an example of a
method for producing the oxynitride film according to this
embodiment. In the present disclosure, the oxynitride film and the
method for producing the oxynitride film are not limited to a
specific production apparatus. In the present disclosure, each step
of a production method may be performed on the basis of a
predetermined program stored in a production apparatus or may be
performed by manually operating a production apparatus.
[2-1. Overall Flow]
[0038] FIG. 2A is a flowchart showing an example of the method for
producing the oxynitride film according to this embodiment. As
shown in FIG. 2A, the method includes a step S1 of supplying the
first precursor, which contains the network formers, into the
reactor 2; a step S2 of supplying an oxygen gas and/or an ozone gas
into the reactor 2; a step S3 of supplying the second precursor,
which contains the alkaline-earth metal, into the reactor 2; and a
step S4 of supplying the ammonia gas and/or a nitrogen gas into the
reactor 2. The method further includes, for example, a step of
supplying a purge gas into the reactor 2.
[0039] The order of these steps, the timing of these steps, and the
number of times these steps are performed are not particularly
limited. For example, a flow shown in FIG. 2A may be repeatedly
performed. For example, some of these steps may be concurrently
performed. For example, the step S1 is performed at least once
before the step S2 or S4. For example, the step S1 and the step S3
are performed in different periods.
[0040] In the case of the order shown in FIG. 2A, the first
precursor is oxidized in the step S2. This allows a skeleton
composed of the network formers bonded to each other to be
obtained. In the step S3, the alkaline-earth metal is bonded to the
skeleton. In the step S4, a nitrogen purge is carried out, whereby
the oxynitride film is obtained.
[0041] The step S2 may be performed between the step S3 and the
step S4 again. The second precursor is oxidized by performing the
second step S2.
[2-2. Preparation]
[0042] Before the production of the oxynitride film is started, a
substrate is placed in the reactor 2.
[0043] A material for the substrate is, for example, metal,
semiconductor, a metal oxide, resin, glass, or ceramic. The metal
may be, for example, Au. The metal oxide may be, for example, a
metal composite oxide. Examples of the resin include polyester,
polycarbonate, a fluorocarbon resin, and an acrylic resin. Examples
of the glass include soda-lime glass and quartz glass. Examples of
the ceramic include aluminum oxide, gallium nitride, sapphire, and
silicon carbide. For example, a thermal oxide (SiO.sub.2) with a
thickness of 400 nm may be formed on a Si substrate.
[0044] The temperature in the reactor 2 is not particularly limited
and may be 250.degree. C. to 550.degree. C., 300.degree. C. to
500.degree. C., or 320.degree. C. to 480.degree. C. When the first
precursor and/or the second precursor contains carbon, setting the
temperature in the reactor 2 to 250.degree. C. or higher enables
the first precursor and/or the second precursor to be appropriately
burned.
[2-3. Supply of First Precursor]
[0045] In the step S1, the first precursor, which contains the
network formers, is supplied into the reactor 2. For example, the
valve V1 is opened, whereby the first precursor is supplied into
reactor 2 from the first precursor supply section 3 as shown in
FIG. 1.
[0046] The temperature of the first precursor supply section 3 is
not particularly limited and may be 1.degree. C. to 50.degree. C.
or 5.degree. C. to 45.degree. C. when the vapor pressure of the
first precursor is high.
[0047] In the step S1, an auxiliary gas may be supplied to the
reactor 2 from the auxiliary gas supply section 7 by opening the
manual valve MV1. The auxiliary gas sweeps the first precursor,
released into the first pipe P1 from the first precursor supply
section 3, to the reactor 2. The flow rate of the auxiliary gas is
not particularly limited and may be 20 ml/min to 60 ml/min or 25
ml/min to 50 ml/min. In the step S1, the flow rate of the first
precursor may be controlled by adjusting the opening of the needle
valve NV. The opening of the needle valve NV is, for example, 10%
to 60%.
[0048] In the step S1, the auxiliary gas may be supplied to the
reactor 2 from the auxiliary gas supply section 8 by opening the
valve V2 depending on the type of the first precursor. The
auxiliary gas sweeps the first precursor into the reactor 2. The
flow rate of the auxiliary gas can be controlled by the mass flow
controller 5a. The temperature of the auxiliary gas supplied from
each of the auxiliary gas supply sections 7 and 8 is not
particularly limited and may be 100.degree. C. to 300.degree. C. or
120.degree. C. to 280.degree. C.
[0049] The auxiliary gas is, for example, an inert gas. Examples of
the inert gas include an argon gas and a nitrogen gas. The
auxiliary gas may be a single type of gas or a mixture of two or
more types of gases.
[0050] The term "network former" refers to atoms or atom groups
(i.e. functional groups) which are directly or indirectly bonded
with each other to form a network structure or which have already
formed the network structure. The network structure is the skeleton
of the oxynitride film. The network formers may be, for example,
portions of a molecule of the first precursor. Another portion of
this molecule may be separated when the network structure is
formed. The network formers contain phosphorus.
[0051] The first precursor is not particularly limited and is, for
example, a phosphorus-containing compound. Examples of the
phosphorus-containing compound include tris(dimethylamino)phosphine
(TDMAP), trimethylphosphine (TMP), triethylphosphine (TEP), and
tert-butylphosphine (TBP). These compounds may be used alone or in
combination.
[0052] The step S1 is finished by closing the valve V1. The
duration of the step S1 is not particularly limited and may be
about 0.01 seconds to 10 seconds, about 0.05 seconds to 8 seconds,
or about 0.1 seconds to 5 seconds.
[2-4. Supply of Oxygen]
[0053] In the step S2, the oxygen gas and/or the ozone gas is
supplied into the reactor 2. For example, the valve V5 is opened,
whereby the oxygen gas and/or the ozone gas is supplied into the
reactor 2 from the oxygen supply section 12 as shown in FIG. 1.
[0054] The oxygen gas may contain, for example, oxygen radicals
produced by a plasma treatment. Plasma ALD enables reactivity to be
increased and also enables the temperature of a system to be
reduced.
[0055] The ozone gas may be produced in such a manner that, for
example, oxygen is supplied to an OT-020 ozone generator available
from Ozone Technology as described in U.S. Patent Application
Publication No. 2011/0099798 A1.
[0056] The flow rate of the oxygen gas and/or the ozone gas is
controlled by the mass flow controller 5c and may be, for example,
20 ml/min to 60 ml/min or 30 ml/min to 50 ml/min. The concentration
of the oxygen gas and/or the ozone gas is not particularly limited
and may be, for example, 100%. The temperature of the oxygen gas
and/or the ozone gas is not particularly limited and may be, for
example, 100.degree. C. to 300.degree. C. or 120.degree. C. to
280.degree. C.
[0057] The step S2 is finished by closing the valve V5. The
duration of the step S2 corresponds to the time from opening the
valve V5 to closing the valve V5. The duration of the step S2 is
not particularly limited and may be about 0.1 seconds to 15
seconds, about 0.2 seconds to 10 seconds, or about 0.2 seconds to 8
seconds.
[2-5. Supply of Second Precursor]
[0058] In the step S3, the second precursor, which contains the
alkaline-earth metal, is supplied into the reactor 2. For example,
the valve V3 is opened, whereby the second precursor is supplied
into the reactor 2 from the second precursor supply section 4 as
shown in FIG. 1.
[0059] The temperature of the second precursor supply section 4 is
not particularly limited and may be 90.degree. C. to 190.degree. C.
or 95.degree. C. to 180.degree. C. when the vapor pressure of the
second precursor is low.
[0060] In the step S3, the auxiliary gas may be supplied to the
reactor 2 from the auxiliary gas supply section 9 by opening the
manual valve MV2. The auxiliary gas sweeps the second precursor,
released into the second pipe P2 from the second precursor supply
section 4, to the reactor 2. The flow rate of the auxiliary gas is
not particularly limited and may be 20 ml/min to 60 ml/min or 30
ml/min to 55 ml/min.
[0061] In the step S3, the auxiliary gas may be supplied to the
reactor 2 from the auxiliary gas supply section 10 by opening the
valve V4 depending on the type of the second precursor. The
auxiliary gas sweeps the second precursor to the reactor 2. The
flow rate of the auxiliary gas can be controlled by the mass flow
controller 5b. The flow rate of the auxiliary gas is not
particularly limited and may be 1 ml/min to 30 ml/min or 5 ml/min
to 20 ml/min.
[0062] The temperature of the auxiliary gas supplied from each of
the auxiliary gas supply sections 9 and 10 is not particularly
limited and may be 100.degree. C. to 300.degree. C. or 120.degree.
C. to 280.degree. C.
[0063] The auxiliary gas supplied from each of the auxiliary gas
supply sections 9 and 10 may be substantially the same as that
exemplified in the description of the step S1.
[0064] The second precursor is a substance containing the
alkaline-earth metal. Examples of the alkaline-earth metal include
Be, Mg, Ca, Sr, Ba, and Ra. The alkaline-earth metal contains, for
example, Mg.
[0065] The second precursor is not particularly limited. Examples
of the second precursor include bis(cyclopentadienyl) magnesium
(Cp.sub.2Mg), bis(methylcyclopentadienyl) magnesium (MeCp.sub.2Mg),
and bis(ethylcyclopentadienyl) magnesium (EtCp.sub.2Mg). These
compounds may be used alone or in combination.
[0066] The step S3 is finished by closing the valve V3. The
duration of the step S3 corresponds to, for example, the time from
opening the valve V3 to closing the valve V3. The duration of the
step S3 is not particularly limited and may be about 0.01 seconds
to 10 seconds, about 0.05 seconds to 8 seconds, or about 0.1
seconds to 5 seconds.
[2-6. Supply of Nitrogen]
[0067] In the step S4, the ammonia gas and/or the nitrogen gas is
supplied into the reactor 2. For example, the valve V6 is opened,
whereby the ammonia gas and/or the nitrogen gas is supplied into
reactor 2 from the nitrogen supply section 13 as shown in FIG.
1.
[0068] The nitrogen gas may contain, for example, nitrogen radicals
produced by a plasma treatment. Plasma ALD enables reactivity to be
increased and also enables the temperature of a system to be
reduced.
[0069] The flow rate of the ammonia gas and/or the nitrogen gas is
controlled by the mass flow controller 5d. The flow rate of the
ammonia gas and/or the nitrogen gas may be, for example, 20 ml/min
to 60 ml/min or 30 ml/min to 50 ml/min. Alternatively, the flow
rate of the ammonia gas and/or the nitrogen gas may be 100 ml/min
to 200 ml/min. The concentration of the ammonia gas and/or gas
serving as a nitrogen supply source is not particularly limited and
may be, for example, 100%. The temperature the ammonia gas and/or
the gas serving as the nitrogen supply source is not particularly
limited and may be, for example, 100.degree. C. to 300.degree. C.
or 120.degree. C. to 280.degree. C.
[0070] The step S4 is finished by closing the valve V6. The
duration of the step S4 corresponds to the time from opening the
valve V6 to closing the valve V6. The duration of the step S4 is
not particularly limited and may be about 0.1 seconds to 15
seconds, about 0.2 seconds to 10 seconds, or about 0.2 seconds to 8
seconds.
[2-7. Supply of Purge Gas]
[0071] In the steps S11 to S14, the purge gas is supplied into the
reactor 2, whereby gases remaining in the reactor 2 are purged. For
example, the valve V7 is opened, whereby the purge gas is supplied
into the reactor 2 from the purge gas supply section 14 as shown in
FIG. 1.
[0072] The flow rate of the purge gas is controlled by the mass
flow controller 5e and may be, for example, 20 ml/min to 60 ml/min
or 30 ml/min to 50 ml/min. The temperature of the purge gas is not
particularly limited and may be, for example, 100.degree. C. to
300.degree. C. or 120.degree. C. to 280.degree. C.
[0073] Each of the steps S11 to S14 may be performed, for example,
after a corresponding one or a specific one of the steps S1 to S4
is completed. Alternatively, each of the steps S11 to S14 may be
performed concurrently with at least one of the steps S1 to S4. For
example, in order to sufficiently remove gases in the reactor 2,
one of the steps S11 to S14 may be continuously performed as a
background process until the formation of the oxynitride film is
completed after the formation of the oxynitride film is
started.
[0074] The duration of each of the steps S11 to S14 is not
particularly limited and may be about 0.1 seconds to 20 seconds,
about 0.5 seconds to 15 seconds, or about 1.0 second to 10
seconds.
[0075] The purge gas is, for example, an inert gas. The inert gas
is, for example, an argon gas and/or a nitrogen gas. The purge gas
may be a single type of gas or a mixture of two or more types of
gases.
[2-8. Supply of Ammonia Gas]
[0076] The method for producing the oxynitride film according to
this embodiment may further include a step of supplying the ammonia
gas into the reactor 2 in addition to the step S4. The step of
supplying the ammonia gas may be performed concurrently with at
least one selected from the group consisting of the steps S1 to S3
and S11 to S14. This enables nitrogen to be stably introduced into
the oxynitride film and also enables the percentage of nitrogen in
the oxynitride film to be increased.
[0077] Alternatively, the step S4 may be a step of supplying the
ammonia gas into the reactor 2 and may be performed concurrently
with at least one selected from the group consisting of the steps
S1 to S3 and S11 to S14.
[0078] In this case, for example, the valve V6 is opened, whereby
the ammonia gas is supplied into reactor 2 as shown in FIG. 1. For
example, the valve V6 may be consistently open until the formation
of the oxynitride film is completed after the formation of the
oxynitride film is started. The flow rate of the ammonia gas is not
particularly limited and may be, for example, 30 ml/min to 100
ml/min or 50 ml/min to 100 ml/min. The concentration of the ammonia
gas is not particularly limited and may be, for example, 100%. The
temperature of the ammonia gas is not particularly limited and may
be 100.degree. C. to 200.degree. C. The temperature of the ammonia
gas may be 180.degree. C. to 200.degree. C. for the purpose of
reducing the decrease in temperature of the reactor 2. The supply
time of the ammonia gas is not particularly limited.
[2-9. Degree of Vacuum in Reactor and Temperature of Pipes]
[0079] In the method for producing the oxynitride film according to
this embodiment, the degree of vacuum in the reactor 2 may be
controlled. The degree of vacuum in the reactor 2 can be controlled
by adjusting, for example, the opening of the manual valve MV3 for
evacuation as shown in FIG. 1.
[0080] The degree of vacuum in the reactor 2 is set depending on
the type of the oxynitride film and may be, for example, 0.1 Torr
to 8.0 Torr or 0.5 Torr to 5.0 Torr. Setting the degree of vacuum
in the reactor 2 to 0.1 Torr or more allows, for example, the first
precursor to be continuously supplied into the reactor 2, whereby
the first precursor is sufficiently oxidized. Therefore, for
example, when the first precursor contains carbon, the amount of
carbon in the oxynitride film can be reduced by sufficient
oxidation. Setting the degree of vacuum in the reactor 2 to 8.0
Torr or less allows, for example, the supply of the second
precursor to be appropriately controlled. The degree of vacuum in
the reactor 2 can be measured with, for example, a Pirani gauge,
TPR280 DN16 ISO-KF, available from PFEIFFER VACUUM.
[0081] In the method for producing the oxynitride film according to
this embodiment, the temperature of each pipe may be set, for
example, as below.
[0082] Referring to FIG. 1, for example, the temperature of the
first pipe P1 and the temperature of the second pipe P2 are set
higher than the boiling point or sublimation temperature of the
first precursor and higher than the boiling point or sublimation
temperature of the second precursor. When the first precursor is,
for example, tris(dimethylamino)phosphine, the boiling point of the
first precursor is about 48.degree. C. to 50.degree. C. When the
second precursor is, for example,
bis(ethylcyclopentadienyl)magnesium, the boiling point of the
second precursor is about 65.degree. C.
[0083] For example, the temperature of the first pipe P1 is higher
than the temperature of the first precursor supply section 3 and
the temperature of the second pipe P2 is higher than the
temperature of the second precursor supply section 4. This enables
the solidification of the first precursor in the first pipe P1 to
be prevented and also enables the solidification of the second
precursor in the second pipe P2 to be prevented.
[0084] The temperature of the first pipe P1 and the temperature of
the second pipe P2 may be 55.degree. C. or more higher than the
temperature of the first precursor supply section 3 and may be
55.degree. C. or more higher than the temperature of the second
precursor supply section 4. The temperature of the first pipe P1
and the temperature of the second pipe P2 may be 60.degree. C. or
more higher than the temperature of the first precursor supply
section 3 and may be 60.degree. C. or more higher than the
temperature of the second precursor supply section 4.
[0085] When the temperature of the first precursor supply section 3
is, for example, 35.degree. C., the temperature of the first pipe
P1 may be set to about 110.degree. C. When the temperature of the
second precursor supply section 4 is 100.degree. C., the
temperature of the second pipe P2 may be set to about 180.degree.
C.
[2-10. Repetitive Treatment]
[0086] FIG. 2B is a flowchart showing an example of a method for
producing an oxynitride film according to an embodiment. The method
shown in FIG. 2B includes a step S1 of supplying the first
precursor into the reactor 2, a step S2 of supplying the oxygen gas
and/or the ozone gas into the reactor 2, a step S3 of supplying the
second precursor into the reactor 2, a step S4 of supplying the
ammonia gas and/or the nitrogen gas into the reactor 2, steps S11
to S14 of supplying the purge gas into the reactor 2, and a step S5
of judging whether the number of repetitions has reached a preset
value. This allows a cycle including the steps S1 to S5 and S11 to
S14 to be repeated a plurality of times. For FIG. 2B, matters
described with reference to FIG. 2A will not be described in
detail.
[0087] In the method shown in FIG. 2B, after each of the steps S1
to S4 is completed, a corresponding one of the steps S11 to S14 is
performed.
[0088] In the example shown in FIG. 2B, whether the number of
repetitions has reached the preset value is judged in the step S5.
In the case where the number of repetitions has not reached the
preset value (NO in the step S5), the cycle returns to the step S1.
In the case where the number of repetitions has reached the preset
value (YES in the step S5), the formation of the oxynitride film is
completed.
[0089] The number of repetitions of the cycle is not particularly
limited and is appropriately set depending on, for example, the
target thickness of the oxynitride film, the type of the first
precursor, and the type of the second precursor. The number of
repetitions of the cycle may be, for example, about 2 to 8,000 or
about 5 to 3,000. In the case where the thickness of the oxynitride
film is adjusted to, for example, about 500 nm, the number of
repetitions of the cycle may be set to 1,000 to 2,000.
Alternatively, in the case where the thickness of the oxynitride
film is adjusted to 50 nm or less, the number of repetitions of the
cycle may be set to 150 or less.
[0090] In the present disclosure, the term "repetition" is not
limited to the case where each step is completed in one cycle. For
example, in the case where the ammonia gas is continuously supplied
into the reactor 2 until the formation of the oxynitride film is
completed after the formation of the oxynitride film is started,
the step is not completed in one cycle but is continuously
performed over a plurality of cycles. In the present disclosure,
the term "repetition" may include this case.
[0091] In this embodiment, the thickness of the oxynitride film is
not particularly limited. The thickness of the oxynitride film may
be, for example, 5 .mu.m or less, 2 .mu.m or less, 550 nm or less,
or 300 nm or less. The thickness of the oxynitride film may be, for
example, 200 nm or less, 150 nm or less, 110 nm or less, 100 nm or
less, or 50 nm or less. The lower limit of the thickness of the
oxynitride film is not particularly limited and may be 0.1 nm or
more or 1 nm or more.
[0092] In the example shown in FIG. 2B, each of the steps S1 to S4
is performed once in one cycle. The number of times each of the
steps S1 to S4 is performed in one cycle is not limited to one. The
number of times each of the steps S11 to S14 is performed and the
timing of each of the steps S11 to S14 are not limited to the
example shown in FIG. 2B.
[0093] Whether the formation of the oxynitride film is continued or
is finished may be judged on the basis of a condition different
from the number of repetitions. The formation of the oxynitride
film may be finished on the basis that, for example, the elapsed
time reaches a predetermined value or on the basis that, for
example, the thickness of the oxynitride film reaches a
predetermined value.
[0094] The relative proportion of each element in the oxynitride
film can be controlled depending on, for example, the flow rate of
the first precursor, the duration of a pulse of the first
precursor, the flow rate of the second precursor, the duration of a
pulse of the second precursor, and the duration of a pulse of the
purge gas. The relative proportion of each element in the
oxynitride film may be controlled in such a manner that, for
example, the flow rate of one of the first and second precursors
that has a lower vapor pressure is set and the flow rate of another
element gas and the duration of a pulse of this element gas are set
on the basis of the flow rate of one of the first and second
precursors that has a lower vapor pressure.
[2-11. Method for Producing MgPON Film]
[0095] An example of a method for producing an oxynitride film, an
MgPON film, will be described below. Matters described with
reference to FIG. 2A or 2B will not be described in detail.
[0096] A method for producing the MgPON film includes, for example,
a step S1 of supplying a first precursor containing phosphorus into
the reactor 2, a step S2 of supplying an oxygen gas and/or an ozone
gas into the reactor 2, a step S3 of supplying a second precursor
containing magnesium into the reactor 2, and a step S4 of supplying
an ammonia and/or a nitrogen gas into the reactor 2. These steps
are performed in the order shown in, for example, FIG. 2A.
[0097] Phosphorus in the first precursor binds to oxygen existing
on a surface of a substrate. Oxygen contained in the oxygen gas
and/or the ozone gas supplied in step S2 oxidizes phosphorus on the
substrate surface to form a phosphate skeleton. Magnesium in the
second precursor binds to oxygen in the phosphate skeleton (for
example, coordinate bonding or ionic bonding). Nitrogen contained
in the oxygen gas and/or the nitrogen gas binds to phosphorus in
the phosphate skeleton that is uncombined with oxygen.
[0098] The step S1 is performed at least once before, for example,
the step S3. This allows magnesium to be introduced in such a state
that the phosphate skeleton is present, thereby enabling the
formation of a non-conductive film to be prevented. The step S1 may
be performed at least once before, for example, the step S2 and/or
may be performed at least once before, for example, the step
S4.
[0099] The order of these steps is not limited to those described
above. For example, the step S3 may be performed after the step S2.
The step S3 may be performed after the step S4. The step S3 may be
performed before the step S1. The step S2 may be performed between
the step S3 and the step S4 again. When the method for producing
the MgPON film includes, for example, such a repetitive treatment
as shown in FIG. 2B, the phosphate skeleton is formed in the first
cycle and therefore the order of these steps in the second and
subsequent cycles may be arbitrarily set.
[0100] The phosphate skeleton is formed by performing the step S1
at least once before the step S2. For example, the steps S1, S11,
S2, and S12 are performed in that order as shown in FIG. 2B,
whereby the phosphate skeleton is formed.
[0101] The relative proportion of each element in the MgPON film
can be controlled depending on, for example, the flow rate of the
first precursor, the duration of a pulse of the first precursor,
the flow rate of the second precursor, the duration of a pulse of
the second precursor, and the duration of a pulse of the purge gas.
The relative proportion of each element in the MgPON film may be
controlled in such a manner that, for example, the flow rate of the
second precursor, which has the lowest vapor pressure and contains
magnesium, is set and the flow rate of another element gas and the
duration of a pulse of this element gas are set on the basis of the
flow rate of the second precursor. The amount of magnesium is set
such that the amount of magnesium is sufficient to grow a film and
is not too large and nitrogen can be introduced into the film.
[0102] The temperature in the reactor 2 is set to, for example,
400.degree. C. to lower than 480.degree. C.
[0103] The vapor pressure of the first precursor, which contains
phosphorus, is relatively high and therefore the temperature of the
first precursor supply section 3 may be, for example, about
1.degree. C. to 50.degree. C. or about 5.degree. C. to 45.degree.
C. The temperature of the second precursor supply section 4 may be,
for example, 40.degree. C. to 50.degree. C. The temperature of the
purge gas may be, for example, 150.degree. C. to 250.degree. C. The
temperature of the oxygen gas and/or the ozone gas may be, for
example, 150.degree. C. to 250.degree. C. The temperature of the
ammonia gas and/or the nitrogen gas may be, for example,
150.degree. C. to 250.degree. C. These temperature conditions
enable the uneven formation of the MgPON film to be inhibited. The
flow rate of each gas, the duration of a pulse of the gas, the
purge time, and the like may be appropriately selected from the
above-mentioned conditions.
3. OXYNITRIDE FILM
[0104] An example of the structure of the oxynitride film will be
described below. The oxynitride film may be one produced by, for
example, the above-mentioned method.
[0105] The oxynitride film contains the network formers, which
contain phosphorus, and the alkaline-earth metal.
[0106] A P2p spectrum obtained by the X-ray photoelectron
spectroscopy measurement (XPS measurement) of the oxynitride film
contains a peak component originating from a P--O bond and a peak
component originating from a P--N bond. The peak component
originating from the P--O bond is a peak component appearing at
about 133 eV to 135 eV. The peak component originating from the
P--N bond is a peak component appearing at about 127.5 eV to 130.5
eV.
[0107] The oxynitride film is characterized in that the P2p
spectrum contains the peak component originating from the P--N
bond. This peak component reflects that introduced nitrogen is
appropriately bonded to phosphorus in the oxynitride film. As shown
in various examples below, it is inferred that P--N bonds in the
oxynitride film can enhance the ionic conductivity of an
alkaline-earth metal (for example, magnesium) in the oxynitride
film. Thus, when the P2p spectrum of the oxynitride film shows the
peak component originating from the P--N bond, the oxynitride film
can effectively function as a solid electrolyte.
[0108] In the P2p spectrum, the intensity of the peak component
originating from the P--N bond may be, for example, 0.1% or more of
the intensity of the peak component originating from the P--O
bond.
[0109] An N1s spectrum of the oxynitride film may contain a peak
component originating from triply coordinated nitrogen (--N<)
and a peak component originating from doubly coordinated nitrogen
(--N.dbd.). The intensity of the peak component originating from
triply coordinated nitrogen may be 50% or less, 40% or less, or 30%
or less of the intensity of the peak component originating from
doubly coordinated nitrogen. As used herein, the term "triply
coordinated nitrogen" refers to a nitrogen atom singly bonded to
three atoms and the term "doubly coordinated nitrogen" refers to a
nitrogen atom singly bonded to a single atom and doubly bonded to
another single atom. A nitrogen atom binds to, for example, atoms
making up the network formers.
[0110] The peak component originating from triply coordinated
nitrogen is a peak component appearing at about 399.4 eV. The peak
component originating from doubly coordinated nitrogen is a peak
component appearing at about 397.9 eV.
[0111] When the oxynitride film contains magnesium as an
alkaline-earth metal, an O1s spectrum obtained by the XPS
measurement of the oxynitride film contains a peak component
originating from a P--O bond and a peak component originating from
an Mg--O bond. In the O1s spectrum, the peak component originating
from the P--O bond is a peak component appearing at about 531.8 eV
and the peak component originating from the Mg--O bond is a peak
component appearing at about 529.7 eV.
[0112] It is inferred that the peak component originating from the
Mg--O bond originates from an impurity, such as MgO, produced in
the oxynitride film. Magnesium, which forms MgO or the like, does
not contribute to ionic conduction. Thus, as the intensity of the
peak component originating from the Mg--O bond is lower, ionic
conduction occurs more efficiently in the oxynitride film. Thus,
the intensity of the peak component originating from the Mg--O bond
is preferably lower than the intensity of, for example, the peak
component originating from the P--O bond. The ratio of the flow
rate of the ammonia gas and/or the gas serving as the nitrogen
supply source to the flow rate of an inert gas (for example, an
argon gas) may be set to, for example, 30% or more. This allows the
peak component originating from the P--O bond to be higher than the
intensity of the peak component originating from the Mg--O
bond.
[0113] In the present disclosure, the term "peak component"
includes not only those appearing on an XPS spectrum as peaks but
also those found by fitting the XPS spectrum.
[0114] In the oxynitride film, the ratio N/P of nitrogen to
phosphorus may satisfy, for example, 0.2.ltoreq.N/P<1.
Sufficiently introducing nitrogen enables the ionic conductivity of
the oxynitride film to be increased. An ALD process can increase
the percentage of nitrogen in the oxynitride film as compared to
another process (for example, a sputtering process).
[0115] When the oxynitride film contains magnesium as an
alkaline-earth metal, the ratio Mg/P of magnesium to phosphorus may
satisfy, for example, 1.5.ltoreq.Mg/P. In other words, the ratio
Mg/P in the oxynitride film may be greater than the ratio Mg/P in
magnesium phosphate (Mg.sub.3(PO.sub.4).sub.2). This allows the
amount of magnesium, which is an ion-conducting species, to be
increased.
4. SECONDARY BATTERY
[0116] The oxynitride film can be used as a solid electrolyte 101
for secondary batteries. For example, a secondary battery 100
according to an embodiment includes a positive electrode 102, a
negative electrode 103, and a solid electrolyte 101 containing the
above-mentioned oxynitride. The positive electrode 102 includes a
positive electrode current collector and a positive electrode
active material. The negative electrode 103 includes a negative
electrode current collector and a negative electrode active
material.
[0117] The secondary battery 100 may be, for example, an
all-solid-state secondary battery. In this case, as shown in FIG.
9, the oxynitride film may be interposed between the positive
electrode 102 and the negative electrode 103. When a voltage is
applied between the positive electrode 102 and the negative
electrode 103, ion conduction occurs in the oxynitride film.
Examples of a positive electrode material that can be used include
fluorinated graphite ((CF).sub.n); oxides of metal elements such as
scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr),
manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu),
and zinc (Zn): and halides of the metal elements. Examples of a
negative electrode material that can be used include metals such as
magnesium (Mg), titanium (Ti), and tin (Sn) and alloys containing
the metals.
[0118] In the secondary battery 100, the solid electrolyte 101 may
be the oxynitride film only or a stack obtained by stacking the
oxynitride film and another film. Examples of the other film
include sulfide films and halide films. The solid electrolyte 101
need not be filmy and may be, for example, powder. Thus, in this
embodiment, the term "oxynitride film" may be appropriately
replaced with the term "oxynitride".
[0119] The positive electrode 102 may have an irregular surface.
The solid electrolyte 101 may be a film covering the irregular
surface. The negative electrode 103 may have an irregular surface.
The solid electrolyte 101 may be a film covering this irregular
surface. This allows the contact area between an electrode and the
solid electrolyte to be large and enables the reaction of the
electrode with the solid electrolyte to be activated. A film of the
solid electrolyte 101 is formed by, for example, the
above-mentioned ALD process so as to have a conformal form
following an irregular surface. This allows the solid electrolyte
101 to be formed with few process variations. At least one of the
positive electrode 102 and the negative electrode 103 has, for
example, a porous shape. The solid electrolyte 101 may have a shape
following an irregular surface due to the porous shape.
[0120] The positive electrode active material may be composed of,
for example, a plurality of active material particles. The solid
electrolyte 101 may form films each of which covers the surface of
a corresponding one of the active material particles. The negative
electrode active material may be composed of, for example, a
plurality of active material particles. The solid electrolyte 101
may form films each of which covers the surface of a corresponding
one of the active material particles. This allows the contact area
between an active material and the solid electrolyte 101 to be
large and enables the reaction of the active material with the
solid electrolyte 101 to be activated. For example, the ALD process
allows a source gas to flow between the active material particles
in each step, thereby enabling films of the solid electrolyte 101
to be formed such that each of the solid electrolyte films covers
the surface of a corresponding one of the active material
particles.
[0121] Alternatively, the solid electrolyte 101 may be deposited on
the positive electrode current collector or the negative electrode
current collector.
[0122] In this embodiment, the secondary battery 100 is not limited
to the all-solid-state secondary battery. The secondary battery 100
may include, for example, a liquid electrolyte in addition to the
solid electrolyte 101. The liquid electrolyte is, for example,
Mg(TFSI).sub.2/3G. Herein, Mg(TFSI).sub.2 is magnesium
bis(trifluoromethanesulfonyl)imide and 3G is triethylene glycol
dimethyl ether. The liquid electrolyte may be one obtained by
blending, for example, 0.5 M of Mg(TFSI).sub.2/3G with 1 M of
3G.
5. EXAMPLES
[0123] Examples of the present disclosure are described below.
5-1. Example 1
[0124] An MgPON film in Example 1 was produced using the production
apparatus 1 shown in FIG. 1. Herein, substantially the same
production method as that shown in the flowchart in FIG. 2C except
the step S4.
[0125] Each of the first precursor supply section 3 and the second
precursor supply section 4 was a precursor bottle available from
Japan Advanced Chemicals Ltd. The reactor 2, a sample holder placed
in the reactor 2, the first precursor supply section 3, the second
precursor supply section 4, and various pipes used were made of
stainless steel (SUS316). Ribbon heaters were wound around the
reactor 2, the first precursor supply section 3, the second
precursor supply section 4, and the pipes. These parts were heated
by energizing the ribbon heaters. The temperature of each of these
parts was measured with a thermocouple and was controlled by a
temperature controller. The mass flow controllers 5a to 5e and the
valves V1 to V7 were controlled using a sequencer, MELSEC-Q,
available from Mitsubishi Electric Corporation and a control
program available from Nihon Spread K.K. The mass flow controllers
5c and 5e were SEC-E40 available from HORIBA STEC, Co., Ltd. The
mass flow controller 5d was SEC-N112MGM available from HORIBA STEC,
Co., Ltd. The needle valve NV was a bellows seal valve, SS-4BMG,
available from Swageloc Co. The degree of vacuum in the reactor 2
was measured with a Pirani gauge, TPR280 DN16 ISO-KF, available
from PFEIFFER VACUUM. The degree of vacuum in the reactor 2 was
controlled at 10.sup.-1 Pa to 10.sup.-3 Pa during film formation by
adjusting the opening of the manual valve MV3.
[0126] A substrate used was a glass substrate provided with Au
electrodes. The Au electrodes were comb-shaped electrodes with a
pitch of 5 .mu.m. The glass substrate provided with the Au
electrodes was placed in the reactor 2. A first precursor used was
tris(dimethylamino)phosphine (TDMAP). A second precursor used was
bis(ethylcyclopentadienyl) magnesium. A purge gas used was an argon
gas. The oxygen supply section 12 was capable of supplying an
oxygen gas. The nitrogen supply section 13 was capable of supplying
an ammonia gas. The temperature in the reactor 2 was set to
450.degree. C. The temperature of the first precursor supply
section 3 was set to 40.degree. C. The temperature of the second
precursor supply section 4 was set to 40.degree. C. The temperature
of the first pipe P1 was set to 170.degree. C. The temperature of
each of all pipes other than the first and second pipes P1 and P2
was set to 200.degree. C. The flow rate of the oxygen gas, the flow
rate of the ammonia gas, and the flow rate of the purge gas were
set to 50 ml/min, 100 ml/min, and 30 ml/min, respectively. The
manual valves MV1 and MV2 were consistently open. The flow rate of
an auxiliary gas supplied from each of the auxiliary gas supply
sections 7 and 9 was set to 50 ml/min. The opening of the needle
valve NV was 37.5%.
[0127] Before the step S1 shown in FIG. 2C was performed, a
preparation step below was performed.
[0128] The valve V7 was opened, the purge gas was supplied into the
reactor 2 from the purge gas supply section 14 for about 1,800
seconds, and the valve V7 was then closed. Next, the valve V5 was
opened, the oxygen gas was supplied into the reactor 2 from the
oxygen supply section 12 for 6 seconds, and the valve V5 was then
closed. Thereafter, a purge step was performed for 8 seconds. After
the preparation step was performed, a repetitive cycle shown in
FIG. 2C was performed 5,000 times. A feed material and the
treatment time of each step in the repetitive cycle are shown in
Table 1 below. Incidentally, the method used in this example was
different from the flowchart shown in FIG. 2C in that the step S4
was continuously performed from the start to end of film formation.
In particular, the valve V6 was opened simultaneously with the
start of the first cycle and was closed simultaneously with the end
of the 5,000th cycle. The flow rate of the ammonia gas was 100
ml/min. The temperature of the ammonia gas was 200.degree. C. In
the step S1, the duration of a pulse of TDMAP was 1 second. In the
step S2, the duration of a pulse of the oxygen gas was 6 seconds.
In the step S3, the duration of a pulse of EtCP.sub.2Mg was 2.5
seconds. In the steps S11 to S14, the duration of a pulse of the
argon gas was 8 seconds, that is, the purge time was 8 seconds. An
interval of 1 second was provided between the steps S13 and
S14.
TABLE-US-00001 TABLE 1 Feed material or Pulse time or Step feed gas
purge time (1) Step S1 TDMAP 1 second (2) Step S11 Ar gas 8 seconds
(3) Step S2 O.sub.2 gas 6 seconds (4) Step S12 Ar gas 8 seconds (5)
Step S3 EtCP.sub.2Mg 2.5 seconds (6) Step S13 Ar gas 8 seconds (7)
Step S2 O.sub.2 gas 6 seconds (8) Step S14 Ar gas 8 seconds (9)
Step S4 NH.sub.3 1 second (10) Step S15 Ar gas 8 seconds
5-2. Example 2
[0129] An MgPON film in Example 2 was produced under substantially
the same conditions as those used in Example 1 except that the
number of repetitive cycles was 999, the degree of vacuum during
film formation was lower than that described in Example 1, the flow
rate of an ammonia gas was increased, and the step S2 directly
after the step S13 and the step S14 were omitted. The MgPON film in
Example 2 had the composition Mg.sub.3.5PO.sub.5.9N.sub.0.45.
5-3. XPS Spectra of MgPON Films
[0130] FIGS. 3, 4A, 4B, and 5 show XPS spectra of the MgPON films
in Examples 1 and 2. An XPS system, Quantera SMX, available from
Ulvac-Phi Inc. was used to measure the XPS spectra.
[0131] FIG. 3 shows P2p spectra of the MgPON films in Examples 1
and 2 and magnesium phosphate. In FIG. 3, a continuous line
represents the P2p spectrum of the MgPON film in Example 1, a
dashed line represents the P2p spectrum of the MgPON film in
Example 2, and a long-dashed short-dashed line represents the P2p
spectrum of magnesium phosphate (Mg.sub.3(PO.sub.4).sub.2) as a
comparative example.
[0132] Referring to FIG. 3, each of the P2p spectra of the MgPON
films in Examples 1 and 2 exhibits a peak component originating
from a P--N bond in addition to a peak component originating from a
P--O bond. However, the P2p spectrum of magnesium phosphate
exhibits no peak component originating from a P--N bond.
[0133] In the MgPON films in Examples 1 and 2, ionic conduction was
confirmed as described below. However, it is generally known that
magnesium phosphate exhibits no ionic conduction. Therefore, it is
inferred that a P--N bond contributes to the ionic conduction of an
MgPON film.
[0134] FIG. 4A shows O1s spectra of the MgPON films in Examples 1
and 2. In FIG. 4A, a continuous line represents the O1s spectrum of
the MgPON film in Example 1 and a dashed line represents the O1s
spectrum of the MgPON film in Example 2.
[0135] Referring to FIG. 4A, the O1s spectra of the MgPON films in
Examples 1 and 2 exhibit a peak component originating from a P--O
bond and a peak component originating from an Mg--O bond. In both
of the O1s spectra of the MgPON films in Examples 1 and 2, the
intensity of the peak component originating from the P--O bond is
higher than the intensity of the peak component originating from
the Mg--O bond. In the case where each of the O1s spectra of the
MgPON films in Examples 1 and 2 is normalized with the intensity of
the peak component originating from the P--O bond, the intensity of
the peak component originating from the Mg--O bond in the MgPON
film in Example 1 is lower than the intensity of the peak component
originating from the Mg--O bond in the MgPON film in Example 2.
[0136] FIG. 4B shows O1s spectra of MgPON films in Examples 3 and 4
and an O1s spectra of an MgPON film in a reference example. In FIG.
4B, a continuous line, a dashed line, and a dotted line represent
the O1s spectrum of the MgPON film in Example 3, the O1s spectrum
of the MgPON film in Example 4, and the O1s spectra of the MgPON
film in a reference example, respectively.
[0137] In Examples 3 and 4, the MgPON films were produced under
substantially the same conditions as those used in Example 1 except
that the flow rate of an ammonia gas was different from that used
in Example 1. In particular, the ratio of the flow rate of an
ammonia gas to the flow rate of an argon gas used in Example 3 was
50% and the ratio of the flow rate of an ammonia gas to the flow
rate of an argon gas used in Example 4 was 30%. In the reference
example, the MgPON film was produced under substantially the same
conditions as those used in Example 1 except very little amount of
an ammonia gas was supplied.
[0138] In the O1s spectra of the MgPON films in Examples 3 and 4,
the intensity of a peak component originating from a P--O bond is
higher than the intensity of a peak component originating from an
Mg--O bond as shown in FIG. 4B. The intensity of the peak component
originating from the Mg--O bond in the MgPON film in Example 3 is
lower than the intensity of the peak component originating from the
Mg--O bond in the MgPON film in Example 4. In the O1s spectra of
the MgPON film in the reference example, the intensity of a peak
component originating from a P--O bond is lower than the intensity
of a peak component originating from an Mg--O bond.
[0139] These results show that increasing the flow rate of an
ammonia gas enables a peak component originating from an Mg--O bond
to be reduced. The ratio of the flow rate of the ammonia gas and/or
gas serving as a nitrogen supply source to the flow rate of an
inert gas (for example, an argon gas) may be set to, for example,
30% or more. This allows the intensity of a peak component
originating from a P--O bond to be higher than the intensity of the
peak component originating from the Mg--O bond. The relative
reduction in intensity of the peak component originating from the
Mg--O bond enables the proportion of magnesium, contributing to
ionic conduction, in a film to be increased.
[0140] FIG. 5 shows N1s spectra of the MgPON films in Examples 1
and 2. In FIG. 5, a continuous line represents the N1s spectrum of
the MgPON film in Example 1 and a dashed line represents the N1s
spectrum of the MgPON film in Example 2.
[0141] In the N1s spectra of the MgPON films in Examples 1 and 2, a
value at about 397.9 eV is greater than a value at about 399.4 eV
as shown in FIG. 5. That is, in the N1s spectra of the MgPON films
in Examples 1 and 2, a peak component originating from doubly
coordinated nitrogen is larger than a peak component originating
from triply coordinated nitrogen. Furthermore, the difference
between the peak component originating from doubly coordinated
nitrogen and the peak component originating from triply coordinated
nitrogen in the N1s spectrum of the MgPON film in Example 1 is
larger than the difference between those in Example 2. This is
probably due to the influence of the degree of vacuum during film
formation.
5-4. Measurement of Ionic Conductivity
[0142] The MgPON films in Examples 1 and 2 were measured for ionic
conductivity using an electrochemical measurement system, Modulab,
Solartron Analytical Inc.
[0143] FIG. 6 shows the temperature dependence of the ionic
conductivity of the MgPON films in Examples 1 and 2. Solid circles
represent the measurement results of the MgPON film in Example 1
and open circles represent the measurement results of the MgPON
film in Example 2. As shown in FIG. 6, the ionic conductivity of
the MgPON film in Example 1 is higher than that in Example 2. The
reason for this is inferred as below. First, the peak component
originating from the P--N bond in the P2p spectrum of the MgPON
film in Example 1 is larger than that in Example 2. This shows that
in the MgPON film in Example 1, nitrogen is more appropriately
bonded to phosphorus. Therefore, the MgPON film in Example 1
probably has a structure which is likely to conduct magnesium ions.
Second, the peak component originating from the Mg--O bond in the
O1s spectrum of the MgPON film in Example 1 is larger than that in
Example 2. This shows that in the MgPON film in Example 1, the
amount of impurities such as MgO is small and the amount of Mg,
which contributes to ionic conduction, is large. Third, the peak
component originating from doubly coordinated nitrogen in the N1s
spectrum of the MgPON film in Example 1 is larger than that in
Example 2. This also probably contributes to high ionic
conductivity.
[0144] The activation energy of the MgPON film in Example 1 was
0.645 eV. The activation energy of the MgPON film in Example 2 was
1.34 eV. The activation energy of other solid electrolyte materials
containing magnesium is as follows: for example, the activation
energy of MgZr.sub.4(PO.sub.4).sub.6 is 1.4 eV and the activation
energy of MgHf(WO.sub.4).sub.3 is 0.835 eV. Therefore, the MgPON
films in Examples 1 and 2, as well as that in the reference
example, have a function as a solid electrolyte.
[5-5. Cross-Sectional Shape and Composition Analysis of MgPON
Film]
[0145] A sample including the MgPON film in Example 1 and a pair of
Au electrodes was prepared, followed by applying a direct-current
voltage of 1 V between the Au electrodes at 450.degree. C. for 1
week. Thereafter, a cross section of the sample was observed with a
transmission electron microscope (TEM), HF 2200, available from
Hitachi, Ltd.
[0146] FIG. 7A shows a cross-sectional TEM image of the sample.
FIG. 7B is an enlarged view of a portion surrounded by a dotted
line in FIG. 7A. The thickness of the MgPON film is about 2 .mu.m.
FIG. 8A shows an enlarged view of a portion surrounded by a dotted
line in FIG. 7B.
[0147] Regions R1, R2, and R3 shown in FIG. 7B were analyzed for
composition by energy dispersive X-ray spectroscopy (EDS) using an
analyzer, NORAN System 7 X-ray Microanalysis System, available from
Thermo Fisher Scientific Inc. Each of the regions R1 and R3 was a
region near a corresponding one of the Au electrodes. The region R2
was a central region between the Au electrodes. The regions R1, R2,
and R3 had a size of 50 nm.times.500 nm.
[0148] Table 2 shows measurement results of the ratio (Mg/P) of
magnesium to phosphorus in each region. Each region was measured by
EDS three times. The average of obtained measurements is shown in
"Mg/P Ave." in Table 2.
TABLE-US-00002 TABLE 2 Region Mg/P Mg/P Ave. R1 1.97 1.96 1.96 1.93
R2 1.16 1.15 1.11 1.18 R3 1.21 1.23 1.27 1.21
[0149] As shown in Table 2, the proportion of Mg in the region R1
is high. This shows that Mg is segregated in the region R1.
Referring to FIG. 8, a region surrounded by a dashed line
corresponds to the region R1 and a peripheral region thereof. In
FIG. 8, the region surrounded by the dashed line has lower contrast
than that of the surrounding thereof. This shows that Mg is
segregated in this region.
[0150] The MgPON film in Example 1 was analyzed for depth-wise
composition by X-ray photoelectron spectroscopy (XPS) separately
from EDS analysis. In particular, the MgPON film was measured for
element concentration profile in the depth direction of the MgPON
film using an X-ray photoelectron spectrometer, Quantera SXM,
available from Ulvac-Phi Inc. in such a manner that the XPS
measurement of the MgPON film and the sputtering of the MgPON film
with Ar were alternately repeated. As a result of measurement, the
ratio of magnesium to phosphorus in the MgPON film in Example 1 was
2.0. Differences between measurement results by EDS and measurement
results by XPS are due to the difference between measurement
methods. In either case, the ratio of magnesium to phosphorus in
the MgPON film in Example 1 was 1.5 or more.
* * * * *